This invention relates to mixtures of reactive dyes, in particular to mixtures of reactive dyes containing, as one component, a disazo dye derived from H-acid.
As is well known, reactive dyes contain at least one substituent capable of taking part in a reaction with a group present on a fabric to be dyed during the dyeing operation.
EP-A-0149170 discloses a range of dyes of the formula 
in which one X is hydrogen and the other sulpho, each of Y1 and Y2 independently is a group xe2x80x94CHxe2x95x90CH2, xe2x80x94CH2CH2OSO3H, xe2x80x94CH2CH2SSO3H, xe2x80x94CH2CH2Cl or xe2x80x94CH2CH2OR, and R is a low molecular weight alkanoyl, benzoyl or benzenesulphonyl group, optionally substituted by a C1-4 alkyl, C1-4 alkoxy, halogen, carboxy or sulpho group.
A typical dye has the formula 
EP-A-0149170 refers only to individual dyes, not mixtures thereof.
On the other hand, each of EP-A-0224224, EP-A-0679697, EP-A-0531968, EP-A-0668328 and EP-A-0600322 discloses respective mixtures of dyes, one of which components is a disazo dye derived from H-acid. One particular example of such a dye has the formula 
This dye is available commercially as C.I. Reactive Black 5 and is added to other dyes as a dulling agent where appropriate.
We find surprisingly that the fastness of a dye mixture can be improved if the dye mixture contains, as a component thereof, a dye of the formula (A) 
wherein each of Y1 and Y2, independently, is a vinyl group or a group of the formula xe2x80x94CH2CH2Q in which Q is a leaving group removable under alkaline conditions to provide a vinyl group.
The dye mixture may contain, in addition to component (A), any of a wide range of dyes.
More particularly, the present invention provides a dye mixture comprising a reactive dye of the formula (A), given and defined above; and
at least one reactive dye (B) selected from
(I) a monoazopyrazole dye of the formula 
wherein R1 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a carboxyl group, a chlorine atom, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
R2 is a phenyl or naphthyl group, optionally having a least one substituent thereon, the substituent, or each substituent, independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a chlorine atom, a vinyl sulphonyl group, a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, a group Het and a group L5-Het, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain and L5 is as defined below; and
R6 is a methyl group, an amide group or a carboxyl group or a salt thereof;
each of R40 and R41, independently, is an aryl group selected from phenyl and naphthyl groups, each of which, independently, is optionally substituted by a vinylsulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinylsulphonyl group; or the group Het, where Het is as defined above;
at least one of R1, R2, R40 and R41 being, or having thereon at least one substituent which is, reactive;
each of L1, L2 and L5 independently is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(xe2x95x90O); C(xe2x95x90O)xe2x80x94O; S(xe2x95x90O)2; S(xe2x95x90O)xe2x80x94NH; C(xe2x95x90O)xe2x80x94NH; and NHC(xe2x95x90O)NH; and
each of x, y and z, independently, is zero or 1; and, when the group R1 is substituted by a hydroxy group ortho to the azo group, a metallized derivative thereof;
(II) a monoazo or disazo dye of the formula 
wherein:
Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain;
R3 or each R3, independently, is a chlorine atom, a methyl group, a methoxy group, a sulphonic acid group or a salt thereof, or is an amino, group of the formula 
xe2x80x83in which each of R18 and R19, independently, is hydrogen, chloro, methyl, (C1-4 alkyl) carbonyl, aminocarbonyl, vinylsulphonyl or a group SO2CH2CH2Q1, in which Q1 is as defined above;
R4, or each R4 independently, is hydrogen, a sulphonic acid group or a salt thereof, a C1-8 alkyl (preferably a C1-4 alkyl) group, a C1-4 alkoxy group, a vinyl sulphonyl group or a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, which C1-4 alkyl group or C1-4 alkyl moiety of the C1-4 alkoxy group is optionally interrupted by an oxygen atom to provide an ether group and is optionally substituted by a vinyl sulphonyl group or a group SO2CH2CH2Q2, in which Q2 is as defined above; or R4 (or when q is 2, each R4 independently) is a phenyl group optitonally substituted by at least one sulphonic acid group or a salt thereof or at least one group Het, where Het is as defined above; or R4 is a group Het, where Het is as defined above
R5 is an aryl group selected from phenyl and naphthyl groups each optionally substituted by at least one sulphonic acid group or, a salt thereof or at least one group Het, as defined above;
R20 is a hydrogen atom or a C1-4 alkyl group;
R21 is a hydrogen atom, a C1-4 alkyl group, a sulphonic acid-C1-4 alkyl group, a chloroalkylsulphonyl-C1-4 alkyl group or a group Het, where Het is as defined above;
m is 1 or 2;
p is zero, 1 or 2;
q is zero, 1 or 2;
each of w1 and w2 is zero or 1; and
w3 is 1, 2 or 3; and
when p is zero, q is zero;
at least one of R4, R5, R18, R19, R21 and Het being, or having thereon at least one substituent which is, reactive;
(III) a monoazopyridone dye of the formula 
wherein:
each of R40, R41, L1 and L2 is as defined above;
R7 is optionally present and is a cyano group or the group xe2x80x94CH2SO3H or the group xe2x80x94C(xe2x95x90O)NH2;
each of R24 and R25, independently, is a hydrogen atom, a C1-4 alkyl group, a sulpho-C1-4 alkyl group, or a carboxyl group;
n is 1 or 2;
r is zero or 1; and
each of s1 and s2 is zero or 1; and when R40 is a phenyl or naphthyl group s2 is 1;
at least one of R40 and R41 being, or having thereon at least one substituent which is, reactive;
(IV) a monoazonaphthyl dye of the formula 
wherein:
each of R1, R40, R41, L1, L2, x, y and z is as defined above;
R9 is CH3(Cxe2x95x90O)xe2x80x94, Het (as defined above) or an aryl group selected from phenyl and naphthyl, which Het or aryl group is optionally substituted by at least one substituent, the or each substituent, independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above;
R35 is a C1-4 alkyl or C2-4 alkenyl group, which C1-4 alkyl or C2-4 alkenyl group is optionally substituted by at least one halogen atom, a sulphonic acid group or salt thereof, a chloroalkylsulphonyl group, a vinylsulphonyl group or xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above and which C1-4 alkyl or C2-4 alkenyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof; the group Het (as defined above); or an aryl group selected from phenyl and naphthyl, which Het or aryl group is optionally substituted by at least one substituent, the substituent or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a halogen atom, a hydroxy group, an amino group optionally substituted by at least one methyl or sulphato group, a vinylsulphonyl group, a vinylsulphonyloxyethyl group and a group SO2CH2CH2Q1 in which Q1 is as defined above;
R50 is a vinylsulphonyl group or a group SO2CH2CH2Q1 (in which Q1 is as defined above);
at least one of R1, R9, R35, R40, R41 and R50 is, or has thereon at least one substituent which is, reactive;
L3 is a linking group selected from N(R20), in which R20 is as defined above; CO; COO; NHCO; NHCOM; SO2NH and SO2;
L4 is a linking group selected from N(R21), in which R21 is as defined above, CO, COO, NHCO, NHCONH, SO2N and SO2;
Z is hydroxy, amino or methylamino;
a is zero or 1-4;
b is zero or 1-3;
c is zero or 1;
d is zero, 1 or 2;
e is zero or 1; and
when each of R1 and Z provides a hydroxyl group ortho to the azo group, a metallized derivative thereof;
(V) a disazoaminonaphthyl dye of the formula 
wherein:
each of R1, R40, R41, L1, L2, x, y and z is as defined above;
each of V and W, independently, is NH2 or OH;
R14 is an aryl group selected from phenyl and naphthyl groups optionally having at least one substituent thereon, the substituents, or each substituent independently, being selected from a sulphonic acid group and a salt thereof, a C1-4 alkyl group, a C1-4 alkoxy group, a hydroxy group, a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
each of R51 and R52 independently is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a vinyl sulphonyl group, a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group, or the group Het3, where Het3 is an optionally substituted aromatic heterocyclic reactive group or a reactive group having an aliphatic chain;
each of L3 and L4, independently, is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(xe2x95x90O); C(xe2x95x90O)xe2x80x94O; S(xe2x95x90O)2; S(xe2x95x90O)xe2x80x94NH; C(xe2x95x90O)xe2x80x94NH; and NHC(xe2x95x90O)NH;
each of f, g and h, independently is zero or 1; and
at least one of R14, R40, R41, R51 and R52 is, or has thereon at least one substituent which is, reactive;
(VI) a formazan dye of the formula 
wherein:
each of R16 and R17 independently of one another, each R16 independently of one another and each R17 independently of one another, is a sulphonic acid group or a salt thereof, a vinyl sulphonyl group or a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
each of Het1 and Het2, independently, is an optionally substituted aromatic heterocyclic reactive or non-reactive group or a reactive or non-reactive group having an aliphatic chain; and
each of R60 and R61, independently, is an aryl group selected from phenyl and naphthyl groups each of which is optionally substituted by a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above;
X1 is a sulphonic acid group or a salt thereof or halogen; each of i, j and v, independently, is zero, 1 or 2; and each of k, l, t and u, independently, is zero or 1; and
at least one of R16, R17, R50, R51, Het1 and Het2 is, or has thereon at least one substituent which is, reactive;
(VII) a dye of the formula 
wherein:
each of R1, R2, R3, R4, R20, R21, R40, L1, Het, x, p, q, w1, w2 and w3 is as defined above; and
at least one of R1, R2, R3 R4 R21, R40 and Het is, or has thereon at least one substituent which is, reactive;
(VIII) a disazo dye of the formula 
wherein R55 is an aryl group selected from phenyl and naphthyl groups;
R56 is a sulphonic acid group or a salt thereof or a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q1 in which Q1 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group;
R57 is an amino group or a group NHRA in which RA is a C1-4 alkyl group;
R58 is a sulphonic acid group or a salt thereof;
R59 is a sulphonic acid group or a salt thereof, a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is a leaving group removable under alkaline conditions to provide a vinyl sulphonyl group; or the group R59 is a group Het or a group L10-Het, where Het is an optionally substituted aromatic heterocyclic reactive or non-reactive group;
R65 is a ureido group or a group HNC(xe2x95x90O)RB in which RB is a C1-4 alkyl group;
L10 is a linking group selected from N(R20), in which R20 is hydrogen or C1-4 alkyl; C(xe2x95x90O); C(xe2x95x90O)xe2x80x94O; S(xe2x95x90O)2; S(xe2x95x90O)xe2x80x94NH; C(xe2x95x90O)xe2x80x94NH; and NHC(xe2x95x90O)NH;
y1 is zero, 1, 2 or 3;
y2 is zero, 1 or 2;
y3 is zero or 1; and
y4 is zero or 1; and
at least one of R56 and 59 is a reactive group.
(IX) a dye of the formula 
(X) a metal phthalocyanine dye of the formula 
wherein:
MPc is a metallophthalocyanine chromophore;
each of R70 and R71 independently, is hydrogen or C1-4 alkyl;
B is a hydrocarbon bridging group;
Het is a reactive heterocyclic group;
each of x1, x2 and x3 is a respective average value;
x1+x2+x3=4;
x1 is at least 1
x2 is zero or 1; and
x3 is at least 1; and
(XI) a triphenodioxazine dye of the formula (XI) (or a salt thereof) 
wherein:
each of B1 and B2, independently, is a hydrocarbon bridging group;
U1 is H or SO3H; and
each of T1 and T2, independently, is halo, C1-4 alkyl, or C1-4 alkoxy;
each of R80 and R81 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof;
each of Het1 and Het2 is as defined above; and
at least one of Het1 and Het2 is a reactive group.
Referring to the dye of the formula (A), preferably at least one of Y1 and Y2 is the group xe2x80x94CH2CH2Q and Q is selected from chlorine, bromine, C1-4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, OP(O) (OH)2, C1-4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl) carbonyloxy, (C1-4 dialkyl) amino or a radical of the formula 
where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4 alkyl or benzyl and Anxe2x8ax96 is in each case one equivalent of an anion. More preferably, each of Y1 and Y2 is the group HO3SOCH2CH2.
Referring now to the reactive dye (B), dyes in one preferred range thereof contain a group Het, where Het is an optionally substituted aromatic heterocyclic reactive around derived from a halogen-substituted heterocyclic compound selected from 1,3,5-triazine, quinoxaline, phthalazine, pyrimidine, pyridiazine and 2-(C1-4 alkylsulphonyl) benzothiazole. More preferably, the aromatic heterocyclic reactive group is substituted and at least one substituent is a halogen atom.
An alternative preferred range of reactive dyes (B) contains a group Het, where Het is a reactive group having an aliphatic chain and selected from acryloyl, mono-, di- or trichloroacryloyl, mono-, di- or tri-bromoacryloyl, xe2x80x94COxe2x80x94CClxe2x95x90CHxe2x80x94COOH, xe2x80x94COxe2x80x94CHxe2x95x90CClxe2x80x94COOH, 2-chloropropionyl, 1,2-dichloropropionyl, 1,2-dibromopropionyl, 3-phenylsulfonylpropionyl, 3-methylsulfonylpropionyl, 2-sulfatoethylaminosulfonyl, 2-chloro-2,3,3-trifluorocyclobutylcarbonyl, 2,2,3,3-tetrafluorocyclobutylcarbonyl, 2,2,3,3-tetrafluorocyclobutylsulfonyl, 2-(2,2,3,3-tetrafluorocyclobutyl)acryloyl, 1- or 2-alkyl- or 1- or 2-arylsulfonylacryloyl, or a radical of the formula SO2xe2x80x94Y3, SO2NHxe2x80x94Y3, CONHxe2x80x94L6xe2x80x94SO2xe2x80x94Y3, or NHCONHxe2x80x94L6xe2x80x94SO2xe2x80x94Y3 where L6 is C1-C4-alkylene or phenylene and Y3 is a vinyl group or a group of the formula CH2CH2Q3 in which Q3 is a leaving group removable under alkaline conditions to provide a vinyl group.
It is also preferred that, the reactive dye (B) has at least one of the groups Q1 and Q2 therein and the or each of groups Q1 and Q2 independently is selected from chlorine, bromine, C1-4-alkylsulfonyl, phenylsulfonyl, OSO3H, SSO3H, OP(O)(OH)2, C1-4-alkylsulfonyloxy, phenylsulfonyloxy, (C1-4 alkyl) carboxyloxy, (C1-4 dialkyl) amino or a radical of the formula 
where Z9, Z10 and Z11 are identical or different and are each, independently of one another, C1-4-alkyl or benzyl and Anxe2x8ax96 is in each case one equivalent of an anion.
In a dye mixture wherein the reactive dye (B) is a monoazopyrazole dye of, the formula (I), given and defined above, it is preferred that at least one of the group [(R41xe2x80x94L2)z(R40xe2x80x94L1)y]xR1 and the group R2 has at least one sulphonic acid group substituted thereon and at least the other of the group [(R41xe2x80x94L2)z(R40xe2x80x94L1)y]xR1 and the group R2 has a group xe2x80x94SO2CH2SO2Q2 substituted thereon, Q2 being as defined above.
In respective preferred ranges of the reactive dye (B) of the formula (I)
(i) x is zero and the group R1 is substituted by at least one of a sulphonic acid group and the group xe2x80x94SO2CH2SO2Q1, wherein Q1 is as defined above;
(ii) each of x, y and z is 1, each of L1 and L2 is NH, R40 is the group Het, where Het is a triazine ring substituted by a halogen atom and R41 is an optionally substituted phenyl group.
(iii) each of x and z is 1, y is zero, L2 is NH and R41 is the group Het, where Het is a difluorochloropyrimidinyl group; and
(iv) each of x and z is 1, y is zero, L2 is CONH (in which the nitrogen atom is attached to the group R1 and the carbon to the group R41) and R41 is the group Het, where Het is a 2,3-dichloroquinoxaline group.
In a reactive dye (B) of the formula (I), R2 is preferably a phenyl or naphthyl group substituted by
(i) at least one of a sulphonic acid group and the group xe2x80x94SO2CH2SO2Q2, where Q2 is as defined in claim 1; or
(ii) at least by the group NHxe2x80x94Het, where Het is a is triazine ring substituted by a halogen atom and optionally substituted by the group 
In a reactive dye (B) of the formula (I), the group R1 may be substituted by a hydroxy group ortho to the azo group and the reactive dye (B) may then be in the form of a copper complex.
Reference is now made to a dye mixture wherein the reactive dye (B) is monoazo or disazo dye of the formula (II), given and defined above.
In such a mixture it is preferred that in the reactive dye (B) of the formula (II), when m is 1 and R4 is alkyl, R4 is C1-4 alkyl.
It is also preferred that the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by at least one sulphopic acid group or a salt thereof or by a group Het, wherein Het is a vinylsulphonyl group or a group SO2CH2CH2Q1 in which Q1 is as defined above.
In an especially preferred reactive dye (B) of the formula (II), m is 1, so that the dye is a monoazo dye.
In preferred ranges of monoazo dyes (B) of the formula (II) in a mixture in accordance with the invention,
(i) each of w1, w2, p and q is zero, w3 is at least 2, at least one of the groups R3 is a sulphonic acid group and the group R5 is an aryl group selected from phenyl and naphthyl groups each substituted by a vinylsulphonyl group or a group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above.
(ii) each of w1 and w2 is zero, each of p and q is 1, R21 is hydrogen and R4 is selected from a triazine ring substituted by at least one halogen atom and optionally additionally substituted by an amino group; and a pyrimidine group substituted by at least one halogen atom and optionally additionally substituted by a methyl group;
(iii) each of w1, w2, p and q is 1, R20 is hydrogen, Het is a triazine ring substituted by a halogen atom, R21 is hydrogen and R4 is selected from a phenyl group or a group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above, and a straight or branched C2-4 alkylene chain substituted by a substituent selected from a hydroxyl group; a sulphonic acid group or salt thereof; a vinylsulphonyl group, a group xe2x80x94SO2CH2CH2Q2, where Q2 is as defined above; and a pyrimidinylamino group in which the pyrimidinyl group is substituted by at least one halogen atom and optionally additionally by a methyl group; and which straight or branched C2-4 alkylene group optionally contains a hetero atom selected from O, S and N(H);
(iv) each of w1 and w2 is zero, each of p and q is 1 and each of R21 and R4 is the group OSO3H; and
(v) w1 is zero, w2 is 1, p is 1, q is 1, R21 is hydrogen, R4is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and Het is a non-reactive heterocyclic group of the formula 
An especially preferred dye mixture contains a dye of the formula (44) as the reactive dye (B) of formula (II) 
Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazopyridone dye of the formula (III), given and defined above.
In respective preferred ranges of the reactive dye (B) of the formula (III),
(i) each of r, s1 and s2 is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is selected from a phenyl group substituted by at least one of a chlorine atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group or a group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above; and a straight or branched chain C2-4 alkylene group optionally containing at least one oxygen atom and substituted by a vinylsulphonyl group or a group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above;
(ii) each of r and s1 is 1, s2 is zero, L2 is NH, R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and R40 is a naphtho-(1,2-d)-1,2,3-triazole substituted by at least one sulphonic acid group or salt thereof; and
(iii) each of r1, s1 and s2 is 1, L1 is CONH (in which the carbon atom is attached to the group R40), L2 is NH, R40 is an optionally substituted phenyl group and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group.
Reference is now made to a dye mixture wherein the reactive dye (B) is a monoazonaphthyl dye of the formula (IV), given and defined above.
In one preferred range of such dyes,
(i) x is zero, d is 1 and a or b is 1. More preferably e is zero.
In other preferred respective ranges,
(ii) x is 1, y is zero, z is 1, L2 is NH and R41 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group;
(iii) x is 1, y is zero, z is 1, L2 is CONH (with the carbon atom attached to the group R1 and the nitrogen atom to the group R41) and R41 is a phenyl group substituted by a vinylsulphonyl group or a group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above; and
(iv) each of x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is an aromatic group selected from phenyl and naphthyl groups each substituted by at least one of a sulphonic acid group or a salt thereof, a vinylsulphonyl group and the group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above.
In such ranges (ii)-(iv) of dyes (B) of the formula (IV), more preferably, e is zero.
In other preferred ranges of the reactive dye (B) of the formula (IV),
(v) e is 1, c is zero, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a methyl group;
(vi) e is 1, c is zero, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9) and R9 is a phenyl group optionally substituted by at least one substituent, the or each substituent being selected from methoxy, carboxyethyl, sulphoethyl, carboxyethenyl, 1,2-dibromoalkyl, chloroethylsulphonyl, vinylsulphonyl, a group of the formula xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above and a 2,3-dichloroquinoxaline group.
(vii) e is 1, c is 1, L3 is CONH (where either the nitrogen or carbon atom thereof is attached to the group R9), R9 is a phenyl group substituted at least by the group L4xe2x80x94R35, where L4 is NH and R35 is a vinyl group optionally substituted by a halogen atom or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group; and
(viii) e is 1, c is zero, L3 is N(R20), where R20 is as defined above (and is more preferably a hydrogen atom or a methyl group) and R9 is a vinylsulphonyl group, a group xe2x80x94SO2CH2CH2Q1 wherein Q1 is as defined in claim 1, or a pyrimidinyl group substituted by a halogen atom and optionally additionally substituted by a methyl group.
In yet another preferred range
(ix) e is 1, c is zero, L3 is N(R20), where R20 is as defined above and R9 is a triazine ring substituted by at least one halogen atom. In this range the triazine ring is preferably substituted by two halogen atoms or by one halogen atom and a morpholinyl group.
In another preferred range,
(x) e is 1, c is 1, L3 is N(R20), where R20 is as defined above, L4 is the group R21, where R21 is as defined above, and R35 is selected from a phenyl group optionally substituted by a sulphonic acid group or salt thereof, a halogen atom, a vinylsulphonyloxyalkyl group, a vinylsulphonyl group or the group xe2x80x94SO2CH2CH2Q1, where Q1 is as defined above; and a C1-4 alkyl group optionally substituted by a vinylsulphonyl group, the group xe2x80x94SO2CH2CH2Q1 where Q1 is as defined above, a sulphonic acid group or a salt thereof or a chloroalkylsulphonyl group, which C1-4 alkyl group optionally additionally contains at least one oxygen or sulphur atom in the chain thereof
In dye mixtures containing a reactive dye (B) of the formula (IV) within the above ranges x is preferably zero.
In the reactive dye (B) of the formula (IV), each of the groups R1 and the naphthalene nucleus may be substituted by a respective hydroxyl group ortho to the azo group and the reactive dye (B) may then be in the form of a copper complex thereon.
An especially preferred dye mixture contains a dye of the formula (53) as the reactive dye (B) 
Reference is now made to a dye mixture wherein the reactive dye (B) is a disazo dye of the formula (V), given and defined above. In such dyes, the respective sulphonic acid groups on the naphthalene nucleus are preferably in the 3- and 6-positions (i.e. such dyes are preferably derived from H-acid).
In one preferred range of dyes of the formula
(i) V is amino, W is hydroxy, each of R1 and R14 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinyl sulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above and R14 is optionally additionally substituted by at least one methoxy group.
It is also preferred, especially for one sub-range within the range (i), that each of x and h is zero. Such a range of dyes includes those of the formula (A) and a mixture in accordance with the invention may indeed contain only dyes of the formula (A), one such dye of the mixture being regarded as a dye of the formula (A) and at least one other such dye of the mixture being regarded as a dye of the formula (V).
In an alternative preferred range of dyes of the formula (V), especially for another sub-range within the range (i), at least one of x and h is 1 and more preferably each of x and h is 1.
In a preferred sub-range (ii) of dyes (B) of the formula (V), within the range (i), x, y and z is 1, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In the preferred ranges (i) and (ii) above, more preferably, each of f, g and h is 1, each of L3 and L4 is NH, R51 is a triazine ring substituted by a halogen atom and R52 is a phenyl group substituted by at least one substituent the or each substituent independently being selected from a halogen atom, a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (iii) of reactive dyes (B) of the formula (V), V is amino, W is hydroxy, h is zero and R14 is a naphthaalene group substituted by at least one sulphonic acid group. More preferably, in this range (iii), each of x, y and z is 1, R1 is a phenyl group optionally substituted by a sulphonic acid group or a salt thereof, each of L1 and L2 is NH, R40 is a triazine ring substituted by a halogen atom and R41 is a phenyl group substituted by at least one substituent, the or each substituent independently being selected from a sulphonic acid group or a salt thereof, a vinylsulphonyl group and a group SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (iv) of the reactive dyes (B) of the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NH and R52 is the group Het3, where Het3 is a substituted aromatic heterocyclic group. In this range (iv), more preferably the group Het3 is a pyrimidinyl group substituted by at least one halogen atom and optionally additionally substituted by a methyl group and still more preferably x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above.
In a preferred range (v) of the reactive dyes (B) of the formula (V), V is amino, W is hydroxy, h is 1, f is zero, g is 1, L4 is NHCO (where either the nitrogen or carbon atom thereof is attached to the group R14) and R52 is the group Het3, where Het3 is a reactive group having an aliphatic chain. More preferably, in this range (v), the group Het3 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and still more preferably x is zero and R1 is a phenyl group substituted by a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above.
One especially preferred dye mixture contains a dye of the formula (105) as a dye of the formula (V) 
and more preferably additionally contains a dye of the formula (44) as another dye (B), of the formula (II) 
Another especially preferred dye mixture contains at least one and more preferably both of the dyes of the formulae (163) and (167) 
Reference is now made to a dye mixture wherein the reactive dye (B) is a formazan dye of the formula (VI), given and defined above.
In preferred respective ranges of the reactive dye (B) of the formula (VI)
(i) each of u and v is zero, i is 1, R16 is a sulphonic acid group or a salt thereof, j is 2 and one R17 is a sulphonic acid group or a salt thereof and the other R17 is a vinylsulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above; and
(ii) v is zero, i is 1, R16 is a sulphonic acid group or a salt thereof, j is 1, R17 is a sulphonic acid group, u is 1 and Het1 is a triazine ring substituted by a halogen atom. In one preferred sub-range within the range (ii), each of k and l is zero, t is 1 and R61 is a phenyl group substituted by at least one sulphonic acid group or a salt thereof, while in another preferred sub-range with the range (ii), each of k, 1 and t is 1, each of R60 and R61 independently is a phenyl group substituted by at least one sulphonic acid group or a salt thereof and Het2 is a triazine ring substituted by a halogen atom. In yet another preferred sub-range within the range (ii), each of k and t is zero, l is 1 and Het2 is a reactive group having an aliphatic chain.
Reference is now made to a dye mixture wherein the reactive dye (B) is a dye of the formula (VII), given and defined above.
In one preferred range of such dyes, x is zero and each of p, q, w and w2 is 1. More preferably, in such a range, R1 is a naphthalene ring substituted by at least one sulphonic acid group. It is also preferred that, in such a range, w3 is 1 and R3 is a methoxy group. Moreover, a preferred group of R20 is hydrogen and preferred groups of R21 are hydrogen, methyl and ethyl. A preferred group R4 is a phenyl group substituted by at least one sulphonic acid group.
In another preferred range of such dyes (VII), each of p, q, w1 and w2 is zero. More preferably, in such a range, w3 is 3 and at least one of R3 is a sulphonic acid group. Other groups of R3 are preferably methyl, methoxy, amino or further sulphonic acid groups. It is also preferred that where, in such dyes, x is 1, R1 is a phenyl or naphthyl group substituted by at least one sulphonic acid group, L1 is NH and R40 is a reactive halopyrimidine group, especially a group containing at least one, more especially at least two fluorine atoms and particularly a difluorochloropyrimidine group, and that where, in such dyes x is zero, R1 is a phenyl groups substituted by a vinyl sulphonyl group or SO2CH2CH2Q1, where Q1 is as defined above and optionally additionally substituted by at least one methoxy group.
Reference is now made to a dye mixture wherein the reactive dye (B) is a disazo dye of the formula (VIII), given and defined above.
In one preferred range of such dyes,
R55 is a naphthyl group;
R56 is a sulphonic acid group or a salt thereof;
R59 is a group L10xe2x80x94Het, where L10 is the group N(H)xe2x80x94 and Het is a reactive heterocyclic group substituted by at least one halogen atom;
y1 is 1, 2 or 3; and
each of y2, y3 and y4 is zero.
A particularly preferred such disazo dye of the formula (VIII) in a dye mixture embodying the invention has the formula 
In another preferred range of such dyes of the formula (VIII)
R55 is a phenyl group;
the group R56 or each group R56 independently is a sulphonic acid group or a salt thereof or is a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above;
y1 is 1 or 2; and
at least one group R56 is a said reactive group or the group R59 is or includes a reactive group.
More preferably, at least one group R56 or the group R59 is a reactive group selected from a vinyl sulphonyl group and a group SO2CH2CH2Q2 in which Q2 is as defined above; or at least one group R56 is a sulphonic acid group or a salt thereof and R59 is the group L10xe2x80x94Het, where L10 is the group N(H)xe2x80x94 and Het is a reactive triazine group substituted by a halogen atom and additionally by the group NHCH2CH2SO3H.
Especially preferred dyes have the formulae 
Reference is now made to a dye mixture wherein the reactive dye (B) is a phthalocyanine dye of the formula (X), given and defined above.
Preferably, in the reactive dye (B) of the formula (X), respective average values of x1, x2 and x3 are x1 is 3, x2 is zero and x3 as 1, three of the four isoindole rings of the phthalocyanine have a respective sulphonic acid substituent (or a salt thereof) thereon and the other isoindole ring has a group SO2NHxe2x80x94Bxe2x80x94NHxe2x80x94Het substituted thereon. More preferably B is a straight or branched C2-4 alkylene group and Het is a triazine ring substituted by at least one halogen atom and optionally additionally substituted by a methoxy group.
Reference is now made to a dye mixture wherein the reactive dye (B) is a triphendioxazine dye of the formula (XI), given and defined above, or a salt thereof.
Preferably, in such a reactive dye (B) of the formula (XI), each of T1 and T2 is a halogen atom, each U1 is a sulphonic acid group or a salt thereof, each of B1 and B2 independently is a straight or branched C2-4 alkylene group, each of Het1 and Het2 independently is a triazine ring substituted by a halogen atom and each of R80 and R81 independently is a phenyl group substituted by at least one sulphonic acid group or a salt thereof.
The dyes of the formula (A) can be prepared by diazotising each of the amines (XX) and (XXI) 
wherein each of Y1 and Y2 is as defined above and firstly coupling the diazotised amine (XXI) under strongly acid conditions (pH 1-2) to H-acid to provide an azo group ortho to the amine group and thereafter coupling the diazotised amine (XX) under slightly acidic, neutral or alkaline conditions (pH 6-7) to the H-acid to provide an azo group ortho to the hydroxy group.
The diazotisalion reactions may each be carried out by adjusting the pH of the amine with a buffer to about 5.3-6, adding an aqueous solution of hydrochloric acid and ice to cool to 0-5xc2x0 C. and then adding a sodium nitrite solution.
The coupling reactions may each be carried out by adjusting the pH as described above and allowing reaction to take place at a temperature of from 4 to 8xc2x0 C. for at least 3 hours.
These and other methods of preparing the dyes of the formula (A) are described in EP-A-0149170.
Likewise disazo dyes (B) of the formula (V) may be prepared in an analogous manner. Methods of preparation of such dyes are also disclosed in DE-A-3825658 and DE-A-3622080.
Dyes (B) of the formula (I) may be prepared by the methods disclosed in DE-A-3717667.
Dyes (B) of the formula (II) may be prepared by the method disclosed in DE-A-3927790, DE-A-3515651 and EP-A-0761768.
Dyes (B) of the formula (III) may be prepared by the methods disclosed in U.S. Pat. No. 4,618,671, DE-A-3717814 and DE-A-3829595.
Dyes (B) of the formula (IV) may be prepared by the method disclosed in U.S. Pat. No. 4,841,031, EP-A-0343262 and EP-B-0776947.
Dyes (B) of the formula (VI) may be prepared by the methods disclosed in DE-A-3737536, DE-A-3743236 and DE-A-3840653.
Dyes (B) of the formula (X) may be prepared by the methods disclosed in WO-A-98/49240.
Dyes (B) of the formula (XI) may be prepared by the methods disclosed in DE-A-3423581 and EP-A-0773264.
Examples of dyes (B) of the formula (VII) are CI Reactive Yellow 57, CI Reactive Yellow 106, CI Reactive Yellow 160 and CI Reactive Yellow 167, all commercially available.
A preferred dye mixture in accordance with the invention comprises, by weight of the total weight of the dyes, from 10-99.5% by weight, inclusive of component (A), given and defined above, and from 0.5 to 90% by weight inclusive of component (B), given and defined above. Respective progressively more preferred ranges are as follows:
10-99% by weight, inclusive of component (A) and from 1 to 90% by weight, inclusive of component (B);
from 10-98.5% by weight, inclusive, of component (A) and from 1.5-90% by weight, inclusive, of component (B);
from 10-97% by weight, inclusive, of component (A) and from 3-90% by weight, inclusive, of component (B);
from 10-95% by weight, inclusive, of component (A) and from 5-90% by weight, inclusive, of component (B);
from 10-90% by weight, inclusive, of component (A) and from 10-90% by weight, inclusive, of component (B);
from 15-90% by weight, inclusive, of component (A); from 10-85% by weight, inclusive, of component (B);
from 20-90% by weight, inclusive, of component (A) and from 10-80% by weight, inclusive, of component (B);
from 30-90% by weight, inclusive, of component (A) and from 10-70% by weight, inclusive, of component (B); and
In an especially preferred mixture, component (B) is a mixture of dyes (B).
Mixtures embodying the invention can be prepared by merely mixing the individual dyes or, in some cases, by synthesis using a mixture of diazotising components. This method is especially suitable when component (B) is at least one dye of the formula (V). The dye mixture may be isolated, for example, by spray drying or salting out.
The mixtures can be used to dye or print on substrates containing a hydroxyl group or nitrogen atom, for example, silk, leather, wool, polyamides, polyurethanes and cellulosic materials, especially cotton.
The mixtures provide excellent properties including resistance to modern peroxide based detergents, fastness to repeat washing, good light fastness, excellent wash-off, good build-up, good compatibility of the dyes with one another and a robustness to process variables.
The reactive dye (A) alone gives a navy shade on cotton and may be mixed with at least one yellow, orange, red or blue reactive dye (B) to give a forest green, navy, brown or black shade.
The mixtures have outstanding properties in comparison with known mixtures, for example CI Reactive Black 5, referred to above, which is often used in a mixture with other dyes as a dulling agent.
Preferred embodiments of the invention will now be described in more detail with reference to the following Examples, in which the numbers assigned to the dyes are those given in Table 2 and all parts are by weight unless otherwise stated. In the Examples, dye A has the formula 